Industrial chemistry IICHEM 3112

Chapter one
Coal and Petroleum processing

1. Introduction
Nations around the world already require staggering amounts of energy for use in the
transportation, manufacturing, heating and cooling, and electricity sectors, and energy
requirements continue to increase as more people adopt more energy-intensive lifestyles.

Energy is one of the central issues of the 21st century, and FUELS are the world’s two most
important sources of primary energy. Fuel is a combustible substance, containing carbon as
main constituent, which on proper burning gives large amount of heat, which can be used
economically for domestic and industrial purposes. Eg., Wood, Charcoal, Coal, Kerosene,
Petrol, Producer gas, Oil gas, LPG etc

Coal and Oil describes humanity’s complex relationships with these fuels: the characteristics of
these energy sources, the ways in which they are used, and the technical, social, policy, and
environmental consequences of large-scale coal and oil consumption. Humanity has long
recognized the value of coal. Many people have worked, suffered, and even died to obtain it.
Many of the machines and processes that formerly depended upon coal as an energy
source are now obsolete, but coal is as necessary today as it has ever been.

Chemical Fuels are classified into three class depending on their physical state of matter.

1
 Industrial chemistry IICHEM 3112

Coal is a solid, brittle, combustible, carbonaceous rock formed by the decomposition and
alteration of vegetation by compaction, temperature, and pressure. It varies in color from brown
to black and is usually stratified. The source of the vegetation is often moss and other low plant
forms, but some coals contain significant amounts of materials that originated from woody
precursors.

Generally, Coal is defined as a combustible rock formed from the partially decomposed remains
of plants and animals, and when measured by weight, the principal element of which coal is
formed is carbon and consist hydrogen, oxygen, nitrogen, trace sulfur and phosphorus as well as
trace amounts of other elements, including mineral.

Historically, Coal has been used in many societies throughout the world for a very long
time. Upon his return from China, Marco Polo (1254–1324) described a black stone that burned
like wood. This material, evidently unfamiliar to him, had been used by the Chinese perhaps as
early as 1000 B.C.E. to smelt metal. Romans were mining coal in England by 400 c.e.,
and long before the arrival of Columbus, Native Americans of the Southwest were using coal.
In most early societies, the alternative to coal was wood.

The plant precursors that eventually formed coal were compacted, hardened, chemically altered,
and metamorphosed by heat and pressure over geologic time is suspected that coal was formed
from prehistoric plants that grew in swamp ecosystems. When such plants died, their biomass
was deposited in anaerobic, aquatic environments where low oxygen levels prevented their
reduction (rotting and release of carbon dioxide). Successive generations of this type of plant
growth and death formed deep deposits of unoxidized organic matter that were subsequently
covered by sediments and compacted into carboniferous deposits such as peat or bituminous or
anthracite coal. Evidence of the types of plants that contributed to carboniferous deposits can
occasionally be found in the shale and sandstone sediments that overlie coal deposits.

Coal deposits, usually called beds or seams, can range from fractions of an inch to hundreds of
feet in thickness. Coals are found in all geologic periods from Silurian through Quaternary (the
period of geologic time, 435 million to 410 million years ago. During which the first air
breathing animal and land plants appeared, but the earliest commercially important coals are

2
 Industrial chemistry IICHEM 3112

found in rocks of Mississippian age (Carboniferous in Europe). Coals generally formed either in
basins in fluvial environments or in basins open to marine incursions.

Historically, of course, wood has also been an important source of energy, but there were two
important reasons that some early societies turned to coal.

First, when measured by weight, coal releases more heat when burned than the same amount
of wood. It is difficult to be precise about the amount of heat released by burning coal
because coal’s energy content also called its heating value depends on how much carbon is
in the coal, its moisture content, and the amount of noncombustible solids found in the coal. All
of these characteristics vary widely from one coal deposit to the next.

Second, because wood has a lower heating value than coal, early energy consumers who
depended on wood for heat had to burn a lot of it. In addition to its value as a fuel source,
wood was also used to build houses and ships and many smaller, more delicate objects such as
furniture and musical instruments. (By contrast, coal’s only value was as a fuel.) Consequently,
technologically simple societies often exhausted their supplies of wood.

1.1. Industrial use of coal

The principal use of traded coals worldwide is for electricity generation and steel
manufacture, with other industrial users and domestic consumption making up the
remainder.

Lack of environmental controls in the use of coal in the past has led to both land and air pollution
as well as destruction of habitat.

Modern environmental guidelines and legislation are both repairing the damage of the past and
preventing a re-occurrence of such phenomena. An outline is given of the types of environmental
concerns that exist where coal is utilized, together with the current position on the improvements
in technology in mining techniques, industrial processes and electricity generation emissions.

3
 Industrial chemistry IICHEM 3112

1.2. Origin of coal

Coal originates in swamps. The process of coal formation begins when some of the
remains of the plants and animals that live in the swamps become submerged and partially
decomposed.
Eventually, these remains are covered by the remains of other creatures, and slowly the layers
accumulate. Coal beds reveal a great deal about the history of the ancient swamps in
which they were formed. Some coal beds, for example, reveal that there were occasional
droughts. The vegetation became dry, and the swamps burned before they were again inundated
with water. The proof is that layers of charcoal, the remains of ancient fires, are present in the
coal deposits.
Sometimes a swamp would become flooded. Water would rush over the swamp, leaving a layer
of clay to settle across the top of the partially decomposed plant and animal matter that had
accumulated on the floor of the swamp. Clay cannot be burned and it does not decay.
Consequently, the clay that was deposited millions of years ago is still present in the coal
deposit. Its presence contributes to the ash generated at power stations when the coal is
burned to produce electricity.
Some swamps formed near the ocean. They were regularly inundated with seawater. The ocean
water contained sulfur compounds. Some of the difference between low-sulfur coals and high-
sulfur coals is thought to be determined by whether the swamp water was salty or fresh.
Eventually, the swamps were buried, sometimes beneath thou-sands of feet of sediment.
Meanwhile, water flowed through the deposits. The water deposited still other chemicals,
permanently changing the chemical composition of the coal that would result from this
process. As the remains of the already ancient swamp sank further beneath the surface,
the plant and animal remains were exposed to ever increasing temperatures and pressures.
Over time, the partially decomposed remains of these ancient creatures become coal. This
process is called carbonization.

Coal can form wherever growth of vegetation is abundant enough, and accumulation of the
sediment is scanty enough, that plant material can accumulate in high concentrations and large
quantities before complete decomposition. For this, one has to appeal to extensive swamps,
usually termed coal swamps, either fresh water or sea water (probably mainly fresh water) in

4
 Industrial chemistry IICHEM 3112

climatic conditions conducive to lush growth of vegetation and far from sources of siliciclastic
sediments. Coal originated from the remnants of variousformsof plant life (mosses, ferns,
shrubs,trees, etc.) that flourished in swamps and bogs millions of years ago during prolonged
periods of warm temperatures and abundant rainfall. This accumulated organic matter, known as
peat, was the precursor of coal.
Although the peat may have been altered by bacterial and chemical action, overlying water
excluded oxygen and retarded the rate of decay. This exclusion of oxygen from the peat was
critical for preserving the organic matter. Over time, inorganic sediments accumulated on top of
the deposits of plant debris.
The gradual rising and lowering of the sea level over time led to deposits of peat alternating with
deposits of sand and mud, resulting in the current situation of coal seams interlayered with rock
layers.
A major reaction occurring during coalification is the loss of oxygen (in the form of water)
from the organic material. Thus, as coalification proceeds, the oxygen and hydrogen contents of
the coal decrease, with a concomitant increase in carbon content.
The length of time that these reactions proceed and the temperatures and pressures to which the
organic molecules are exposed determine the degree of coalification (maturity) of the coal
Coal rank is a measure of the degree of coalification; as coalification proceeds, coal rank
increases from lignite through sub-bituminous and bituminous to anthracite.

1.3. Classification of coal

Most coals are classified according to their carbon content and the specific amount of energy that
they contain. The greater the amount of carbon, the higher the effective rank of the coal and the
higher the average energy content of the material.

There are two important characteristics to classify coal that are based on types of coal resulting
from different in proportion of plant ingredient and depending on varieties of composition of
racking. Depending on the various of composition of ranking

5
 Industrial chemistry IICHEM 3112

The least transformed deposits—that is, the deposits that are most similar to the peat from which
they formed—are called lignite, also known as brown coal. As the rank increases, so does the
percentage of fixed carbon. In order of increasing rank, there is subbituminous, bituminous, and
anthracite. Higher ranks of coal are generally harder and shinier than lower ranks and have
somewhat higher heating values.
1.4. Coal mining and preparation

Coal mines fall into two general classifications-surface and underground.

1.4.1. Underground Mining

For many years, coal mining was largely restricted to under-ground mines. During this time, coal
was removed by a technique called room-and-pillar mining. To see how this works, imagine a
coal seam as a large panel-like deposit of material lying more or less horizontally beneath the
ground. Early miners could not remove all of the coal—or even most of it because that
would have created a large underground chamber with no supports for the roof.

6
 Industrial chemistry IICHEM 3112

Underground mining is somewhat more labor-intensive than surface mining and is used to
remove coal located too deep for surface mining; but here too, machines are used in most
instances to dig, load, and haul the coal.
In the 1970s, another method of underground mining, called long wall mining, began to gain
favor. While room-and-pillar mining can be used on deposits that are not horizontal or uniform
in thickness, long wall mining makes essential use of these characteristics.
A drift mine is one that enters a coal seam exposed at the surface on the side of a hill or
mountain. The mine follows the coal horizontally. Today, most underground mining is
accomplished via long wall mining.

A slope mine is one where an inclined tunnel is driven through the overlying rock to the coal,
with the mined coal removed by conveyors or trucks.

A shaft mine is one where a vertical shaft is dug from the surface to reach the coal, which may
be at great depth. The coal is then mined by horizontal entry into the seam, with the recovered
coal hoisted to the surface through the vertical shaft.

1.4.2. Surface Mining

The alternative to underground mining is surface mining. This can be accomplished as long
as the coal seam is not too deep underground, and this is exactly the geology of the
coal deposits in the western United States. To mine these deposits, the rock and dirt that lie
above the deposits, called the “overburden,” is stripped away and enormous machines excavate
the coal from open-air pits. The key to increasing productivity in surface mines is to make
larger pits and use larger machines. The scale of modern surface mining is hard to appreciate
without seeing the mines in action.

Surface mining techniques are used when the coal is present near the surface, and the over lying
strata (overburden) are thin enough to permit economic removal. Surface mining techniques
include contour mining, strip mining, and auger mining.

Contour mining is used in hilly areas, where the slope of the surface will permit only a nar row
bench cut around the side of a hill; the excavation is backfilled immediately after the removal of
coal. It is the only method that can be used on slopes of 15 degrees or higher.

7
 Industrial chemistry IICHEM 3112

Strip miningis used in flat or gently rolling land, predominantly in the Midwest and West, where
large, efficient equipment can be used. In this technique, the coal is exposed by removing the
overburden.Strip mining can be very efficient, especially in the West, where coal seams can be
100 ft thick or more.
Auger miningis a supplementary method used to reach coal in stripped areas where the
overburden has become too thick to be removed economically. Large augers are operated from
the floor of the surface mine and bore horizontally into the coal face to produce some reserves
not otherwise minable. This technique is frequently used to supplement coal recovery from
contour mining.

8
 Industrial chemistry IICHEM 3112

1.5. Coal Utilization

Coal preparation:-is a term applied to up grading coal to make it suitable for a particular use;
this includes blending and homogenization, size reduction, and beneficiation or cleaning.

It is this last aspect, as well as the degree to which it is required, that most significantly governs
the cost of coal preparation. Only about one-third of the3.3 billion metric tons of coal produced
every year is at present cleaned by breaking, crushing, screening, and wet and dry concentrating
processes.

The purpose of coal cleaning" is to remove mineral matter, consisting of rock, slate, pyrite, and
other impurities, and to increase the organic content. Coal cleaning typically involves size
reduction, particle sizing, cleaning, and dewatering.

In general, cleaning processes utilize differences in density or surface properties between the
organic and mineral matter in the coal. Depending upon the size of the coal particles being
cleaned, cleaning techniques can be divided into three areas: coarse, medium, and fine.

1.5.1. Coal Combustion

The simplest use of coal is to burn it for heat. Coal combustion for domestic heating has been
practiced since antiquity. Today the use of coal for domestic heat is a very minor in world
market. Coal was once used as a household heating and cooking fuel in Wester n nations; but it
was largely replaced by natural gas, propane, electricity and fuel oil. Less than 1% of the coal
sold is used for domestic heating and cooking, and only a very small percentage of households
use coal as a primary source of energy.

Coal is still used for household heating and cooking in China, where it is a major source of air
pollution.

In Wester n nations, coal is used primarily as a fuel for large industrial boiler s, especially for
electric power generation. Large user s are able to get more complete combustion, which reduces
odor and soot, and are able to install complex and expensive air pollution equipment.

9
 Industrial chemistry IICHEM 3112

1.5.2. Coal Carbonization (Coking)

Distractive distillation of coal provides coke. Distractive distillation is heating any materials in
high temperature in the absences of air. The second largest use of coal is the manufacture of
coke for the metallurgical industry. Iron and its alloys (particularly the various kinds of steel)
are perhaps the most versatile metallic construction materials known to humankind.

These are two types of carbonizations of coal:

(1) Low-temperature carbonization:

In this process, the heating of coal is carried out at 500 - 700°C. The yield of semi coke is
about 75-80% and it contains about 5-15% volatile matter produce char. It is not
mechanically strong, so it cannot be used as a metallurgical coke. However, it burns easily
giving practically a smokeless, hot and radiant fire. Hence, it is suitable for domestic
purposes.

(2) High-temperature carbonization is carried out at 900 - 1,200°C with the object of producing
coke of the right porosity, hardness, purity, strength, etc., so that it can be used in metallurgy.
Nearly all the volatile matter of coal is driven off and the yield of coke is about 65-75%,
containing only 1-3% volatile matter.

10
 Industrial chemistry IICHEM 3112

Products and by products of distractive distillation of coal

When coal heated about 1000oC it will give different components, such as coke, coal tar,
ammoniacal liquor and coal gas.

Coke is black tough powder material obtained as residue on distractive distillation of coal.

It is used for reducing agent of metallurgical industry. It is pure carbon.

Coal tar is black thicky liquid obtained as by product of distractive distillation of coal. It
contains about a bout 200 substance. It is used as ati dandruff shampoo, perfume, paint and lice
repelling shampoos as well as road maintaining material.

Ammoniacal liquor- the component contains ammonium hydroxide. This component treated
with sulphuric acid to yield ammonium sulphate and used for fertilizer.

Coal gas is the gaseous component of coal such as mixture of carbonamide, methane and
hydrogen gas.

11
 Industrial chemistry IICHEM 3112

1.5.3. Coal gasification

A process for producing natural gas from coal. Coal is heated and brought in contact with steam.
Hydrogen atoms in the vapor combine with coal’s carbon atoms to produce a hydrocarbon
product similar to natural gas. Gasification technologies provide a flexible foundation for high
efficiency, low emissions systems capable of sup-porting coal conversion to a range of energy
and chemical products. Gasification of coal is a process whereby coal is converted to a syngas,
which is predominately a mixture of carbon monoxide and hydrogen. The primary goals of
gasification are:

When the coke treated with steam produce water gas and producer gas. This product which
contains carbon monoxide and hydrogen molecule is called synthesis gas.

Coke (C) + H2O (g)  CO + H2 ----- water/sythn gas.

Coke (C) + O2 + N2 (g)  Co, N2 and H2------- producer gass

1. Convert the entire non-ash fraction of the feed to syngas; mixture of CO/H2

2. Produce gasses that preserve, as much as possible, the heat of combustion value of the
feedstock.

Figure: -
gasification
process of coal

12
 Industrial chemistry IICHEM 3112

Syngas is a precursor to an extensive range of energy and chemical products. The chemical
processes that comprise gasification are considerably different from those which occur in more
traditional coal-combustion based boilers. A fundamental difference is the oxygen to carbon
ratios used: combustion systems typically operate with excess air, whereas gasification systems
use significantly lower oxygen to carbon ratios, and this stoichiometry is carefully controlled to
ensure that optimum gasification conditions are present for the specific fuel–technology
combination. Consequently, the coal combustion reactions have a minor role in the coal
gasification conversion process, and the much slower, endothermic coal gasification reactions
with steam and carbon dioxide dominate the conversion process. As the physical and chemical
reaction processes that constitute the gasification process are vastly different from those found in
coal combustion, a different set of fuel performance and coal characterization criteria are needed.
Gasification reactions are several orders of magnitude slower than the combustion reactions,
making their impact on coal behavior and gasifier design more significant.

1.5.4. Hydrogenation of coal

Coal or hydrogenation of coal involves raising the atomic hydrogen to carbon ratio. Coal
can be converted to liquid and gaseous fuels by direct and indirect processing.
Hydrogenation of coal is also called liquefaction of coal. The source of coal is from various
coal mines.

This method was first proposed by Bergius in Germany. It consists of converting low
grade coals such as bitminuous coal into liquid and gaseous fuels by hydrogenating them
in presence of iron oxide as catalyst. The goal of most coal-to-liquids processes is to convert
coal to a liquid that resembles a petroleum product. Compared to petroleum, coal:

• is a solid

• has a higher molecular weight

13
 Industrial chemistry IICHEM 3112

• has a lower hydrogen/carbon ratio

• has higher concentrations of hetero-atoms: oxygen, sulfur and nitrogen

• contains ash.

Catalytic hydrogenation of coal can produce a petroleum-like product. Hydrogen is added to

carbon carbon double bonds and aromatic rings to produce carbon carbon single bonds. Large
molecules are split, or hydrocracked, to produce lower molecular weight compounds. Oxygen,
sulfur, and nitrogen are removed as water, H2S, and NH3.

Hydrocracking, plus the removal of polar hetero-atoms; converts solid coal into a liquid, with
some byproduct gas. The reaction products mainly contain mixture of petroleum hydrocarbons

Figure:- hydrogenation of coal (source; DAVID A BELL, 2011 )

14
 Industrial chemistry IICHEM 3112

Coal hydrogenation is a potential route to transform coal into other usable compounds
such as methane, benzene and aromatics. Methane otherwise can be converted to an
equivalent liquefied natural gas (LNG) for fuel usage in various automobiles.

1.6. Analysis of coal

Coal has heterogeneity in quality and shape. In collection of samples, therefore, correct and
appropriate amounts of coal samples representative of the coal must be collected. Lot indicates
the unit of coal for which rank is determined.

1.6.1. Proximate Analysis

Moisture: The moisture content is the ratio of decrease in weight that occurs when one gram of a
sample weighed under a constant moisture base is heated at 107 • 2 ~ for 60 min. The moisture
content decreases with increasing coal rank.

Ash: The ash content is measured by the decrease in weight when one gram of a sample is
burned completely at 815 0C

Volatile Matter: The volatile matter content is obtained from the decrease in weight when a
sample in a platinum crucible is heated in an electrical furnace for 7 min at 925 __+ 20 ~

Fixed Carbon: The fixed carbon content is calculated by subtracting the sum of the moisture, ash
and volatile contents from 100.

Importance of proximate analysis

Proximate analysis provides following valuable information’s in assessing the quality of coal:

(1) Moisture: Moisture lowers the effective calorific value of coal. Moreover, it quenches the fire
in the furnace. Hence, lesser the moisture content, better the quality of coal as a fuel. However,
presence of moisture, up to 10%, produces a more uniform fuel-bed and less of "fly-ash".

(2) Volatile matter: A high volatile matter containing coal burns with a long flame, high smoke
and has low calorific value. Hence, lesser the volatile matter, better the rank of the coal. Higher
volatile content in coal is undesirable.

A high volatile matter content means that high-proportion of fuel will be distilled and burned as a
gas or vapour. The volatile matter present in the coal may be combustible gases (such as
methane, hydrogen, carbon monoxide and other hydrocarbons) or non-combustible gases (like
CO2 and N2). Volatile matter content is of special significance in coal gas manufacture and in
carbonization plants, particularly when by-product recovery is the main object. Thus, high-

15
 Industrial chemistry IICHEM 3112

volatile matter containing coals do not cake well; whereas medium-volatile matter content coals
are capable of yielding hard and strong coke on carbonization.

(3) Ash is a useless, non-combustible matter, which reduces the calorific value of coal.
Moreover, ash causes the hindrance to the flow of air and heat, thereby lowering the temperature.
Also, it often causes. Trouble during firing by forming clinker), which block the inters paces of
the grate. This in-turn causes obstruction to air supply; thereby the burning of coal becomes
irregular. Hence, lower the ash content, better the quality of coal. The presence of ash also
increases transporting, handling and storage costs. The presence of ash also causes early wear of
furnace walls, burning of apparatus and feeding mechanism.

(4) Fixed carbon: Higher the percentage of fixed carbon, greater is its calorific and better the
quality coal. Greater the percentage of fixed carbon, smaller is the percentage of volatile matter.
This also represents the quantity of carbon (in coal) that can be burnt by a primary current of air
drawn through the hot bed of a fuel.

1.6.2. Ultimate Analysis

Carbon, Hydrogen: Coal is burned in a combustion tube under an oxygen stream, and car- bon
and hydrogen are oxidized to carbon dioxide and water, respectively.

Sulfur: There are two kinds of sulfur, combustible sulfur and non-combustible sulfur. Total
sulfur indicates the sum of both and is measured by the Eschka method or the combustion
volumetric technique.

Nitrogen: The Kjeldahl method or semi-Kjeldahl method is used for nitrogen determination.

Significance of ultimate analysis

Carbon and hydrogen: Greater the percentage of carbon and hydrogen better is the coal in quality
and calorific value. However, hydrogen is mostly associated with the volatile matter and hence,
it affects the use to which the coal is put. Also higher percentage of carbon in coal reduces the
size of combustion chamber required. The amount of carbon, the major combustible consti1fent
of coal, depends on the type of coal and its percentage increases with rank from lignite to
anthracite. Thus, percentage of carbon forms the basis of classification of coal.

(2) Nitrogen has no calorific value and hence, its presence in coal is undesirable; thus, a good
quality coal should have very little nitrogen content.

16
 Industrial chemistry IICHEM 3112

(3) Sulphur, although contributes to the heating value of coal, yet on combustion produces acids
(S02 and S03), which have harmful effects of corroding the equipments and also cause
atmospheric pollution. Sulphur is, usually, present to the extent of 0.5 to 3.0% and derived from
ores like iron pyrites, gypsum, etc., mines along-with the coal.

Presence of sulphur is highly undesirable in coal to be, used for making coke for iron industry,
since it is transferred to the iron metal and badly affects the quality and properties of steel.
Moreover, oxides of sulphur (formed as combustion products) pollute the atmosphere and leads
to corrosion.

(4) Oxygen content decreases the calorific value of coal. High oxygen-content coals are
characterized by high inherent moisture, low calorific value, and low coking power. Moreover,
oxygen is in combined form with hydrogen in coal and thus, hydrogen available for combustion
is lesser than actual one. An increase in 1% oxygen content decreases the calorific value by
about 1. 7% and hence, oxygen is undesirable. Thus, a good quality coal should have low
percentage of oxygen

1.6.3. Calorific Value (Heating Value)

Calorific value of a fuel is “the total quantity of heat liberated, when a unit mass (or volume) of
the fuel is burnt completely”

The calorific value of coal represents gross calorific value (GCV), which contains the latent heat
of water vaporization. It is the total amount of heat produced, when unit mass/volume of the fuel
has been burnt completely and the products of combustion have been cooled to room
temperature (15° C or 60° F).

It is explained that all fuels contain some hydrogen and when the calorific value of hydrogen
containing fuel is determined experimentally, the hydrogen is converted into steam. If
the products of combustion are condensed to the room temperature, the latent heat of
condensation of steam also gets included in the measured heat which is then called GCV.

When the latent heat of water vaporization is not included, the calorific value is called net
calorific value (NCV). It is the net heat produced, when unit mass/volume of the fuel is
burnt completely and the products are permitted to escape.

17
 Industrial chemistry IICHEM 3112

In actual practice of any fuel, the water vapour and moisture, etc., are not condensed and escape
as such along with hot combustion gases. Hence, a lesser amount of heat is available.

The calorific value of solid or liquid fuels can be determined with the help of bomb calorimeter.

Units of Heat: (1) Calorie- is the amount of heat required to raise the temperature of one gram
of water through one degree centigrade (15-16° C).

(2) Kilocalorie – is equal to 1,000 calories. This is the unit of metric system and may be
defined as “the quantity of heat required to raise the temperature of one kilogram of water
through one degree centigrade. Thus, 1 kcal = 1,000 calories.

(3) British Thermal Unit (BTU)- is defined as “the quantity of heat required to raise
the temperature of one pound of water through one degree Fahrenheit (60-61° F). This is the
English system unit.

1 BTU = 252 cal = 0.252 kcal and 1 kcal = 3.968 BTU

(4) Centigrade heat unit (CHU)-is “the quantity of heat required to raise the
temperature of 1 pound of water through one degree centigrade”. Thus,

1 kcal = 3.968 BTU = 2.2 CHU

Higher or gross calorific value:

Usually, all fuels contain some hydrogen and when the calorific value of hydrogen-containing
fuel is determined experimentally, the hydrogen is converted into steam. If the products of
combustion are condensed to the room temperature (15°C or 60°F), the latent heat of
condensation of steam also gets included in the measured heat, which is then called "higher or
gross calorific value". So, gross or higher calorific value (HCV) is "the total amount of heat
produced, when unit mass/volume of the fuel has been burnt completely and the products of
combustion have been cooled to room temperature"(i.e., 15°C or 60°F).

Lower or net calorific value (LCV)

In actual use of any fuel, the water vapour and moisture, etc., are not condensed and escape as
such along-with hot combustion gases. Hence, a lesser amount of heat is available. So, net or

18
 Industrial chemistry IICHEM 3112

lower calorific value (LCV) is "the net heat produced, when unit mass /volume of the fuel is
burnt completely and the products are permitted to escape".

Net calorific value = Gross calorific value - Latent heat of condensation of water vapour
produced

= GCV - Mass of hydrogen per unit weight of the fuel burnt x 9 x Latent
heat of condensation of water vapour

From the temperature difference, calorific value of the fuel can be calculated as follows:

19
 Industrial chemistry IICHEM 3112

This is based on the fact that 1 part of H by mass gives 9 parts of H2O, and latent heat of steam
is 587 kcal/kg.

2. Liquid Fuels

The important liquid fuels are petroleum, petroleum products, tar, alcohols. These are naturally
found under the sea surface. Liquid fuels are also obtained synthetically from' hydrogenation of
coat. Liquid fuels find extensive use in domestic and industrial fields.

Petroleum

Petroleum or crude oil is a dark greenish brown or black coloured viscous oil found deep in
earth's crust. The oil is usually floating over a brine solution and above the oil, natural gas is
present. Crude oils are principally found in oil reservoirs associated with sedimentary rocks
beneath the earth’s surface.

Petroleum and the equivalent term crude oil cover a wide assortment of materials consisting of
mixtures of hydrocarbons and other compounds containing variable amounts of sulfur, nitrogen,
and oxygen, which may vary widely in volatility, specific gravity, and viscosity.

Crude oil containing mixture of paraffinic, olefinic and aromatic hydrocarbons with minor
amounts of organic compounds like N, 0 and S. The average composition of crude oil is C =80 -
87 %, H =11-15%, S = 0.1 -3.5%, (N +O) =0.1- 0.5%.

a) Classification of petroleum

20
 Industrial chemistry IICHEM 3112

Petroleum is classified into three types based on variation of chemical nature of crude oil
found in the earth.

i) Paraffinic-base type crude oil: It contains saturated hydrocarbons from CH4 to C35H72 and
little amount of naphthalene and aromatics.

ii) Asphaltic-base type crude oil: It contains mainly cycloparaffins or naphthalenes with smaller
amount of paraffins and aromatic hydrocarbons.

iii) Mixed-base type crude oil : It contains both paraffinic and asphaltic hydrocarbons and are
generally in the form of semi-solid waxes.

Petroleum occurs underground, at various pressures depending on the depth. Because of the
pressure, it contains considerable natural gas in solution. Petroleum underground is much more
fluid than it is on the surface and is generally mobile under reservoir conditions because the
elevated temperatures (the geothermal gradient) in subterranean formations decrease the
viscosity.

Petroleum is derived from aquatic plants and animals that lived and died hundreds of millions of
years ago. Their remains mixed with mud and sand in layered deposits that, over the millennia,
were geologically transformed into sedimentary rock. Gradually the organic matter decomposed
and eventually formed petroleum (or a related precursor), which migrated from the original
source beds to more porous and permeable rocks, such as sandstone and siltstone, where it
finally became entrapped. Such entrapped accumulations of petroleum are called reservoirs.

Crude oil is a mixture of literally hundreds of hydrocarbon compounds ranging in size from the
smallest, methane, with only one carbon atom, to large compounds containing 300 and more
carbon atoms. A major portion of these compounds are paraffins or isomers of paraffins. A
typical example is butane shown below:

21
 Industrial chemistry IICHEM 3112

Most of the remaining hydrocarbon compounds are either cyclic paraffins called naphthenes or
deeply dehydrogenated cyclic compounds as in the aromatic family of hydrocarbons. Examples
of these are shown below:

22
 Industrial chemistry IICHEM 3112

The majority of hydrocarbon compounds present in crude oil have been isolated however, but
under delicate laboratory conditions. In refining processes the products are identified by groups
of these hydrocarbons boiling between selective temperature ranges. Not all compounds
contained in crude oil are hydrocarbons. There are present also as impurities, small quantities of
sulfur, nitrogen and metals.

Crude oils are refined to separate the mixture into simpler fractions that can be used as fuels,
lubricants, or as intermediate feedstock to the petrochemical industries.

The crude oil mixture is composed of the following groups:

1. Hydrocarbon compounds (compounds made of carbon and hydrogen).

2. Non-hydrocarbon compounds.

3. Organometallic compounds and inorganic salts (metallic compounds).

Mining and Refining of Petroleum

The crude oil obtained from the earth crust contains water, sulphur and some unwanted
impurities. After removal of water, sulphur and these impurities, the crude oil is separated into
various useful fractions by fractional distillation and finally conveI1ed into desired specific
products having different boiling points. The process is called "Refining of Petroleum" and the
refining plants are called "Oil refineries". The process of refining involves the following steps.

Step -I: Separation of water (Cottrell's process)

The crude oil from the oil well is an extremely stable emulsion 0 f oil and salt water. The crude
oil is allowed to flow between two highly charged electrodes, where colloidal water droplets
coalesce to form large drops, which is then separated out from the oil.

Step - II: Removal of harmful impurities

a) The presence of NaCI and MgCI in the crude oil can corrode the refining equipment, hence
these salts are removed by electrical desalting and dehydration methods.

23
 Industrial chemistry IICHEM 3112

b) The sulphur compounds present in the crude oil is removed by treating oil with copper oxide,
which results in the formation of copper sulphide (solid), which is then removed by filtration.

Step - III: Fractional distillation

The crude oil is then heated to about 400°C in an iron retort, whereby all volatile substances
(except asphalt or coke) are evaporated. The hot vapors are then passed up a fractionating
column, which is a tall cylindrical tower containing a number of horizontal stainless steel trays at
short distances. Each tray is provided with small chimney covered with a loose cap.

When the vapours of the oil go up in the fractionating column, they become gradually cooler and
get condensed at different heights of column. The fractions having higher boiling points
condense at lower trays whereas the fractions having lower boiling points condense at higher
trays. The gasoline obtained by the fractional distillation is called straight --run gasoline

Processing Operations in a Petroleum Refinery

I. Separation process:- the separation of crude oil components through distillation,

In modern refinery practice the distillation of atmospheric residue is accomplished under high
vacuum conditions in a specially designed tower whose internal equipment ensures a very lower
pressure drop. Low boiling fractions vaporize at atmospheric pressure up to a temperature below
400 ° C without cracking the hydrocarbon compounds. High boiling fractions are vaporized
under vacuum at a temperature much lower than 400 ° C and cracking is avoided. Thus, all the
low and high boiling fractions of crude oil are separated by atmospheric distillation followed by
vacuum distillation without cracking or degradation of the original hydrocarbons present in crude
oil. After the removal of oil fractions, the vacuum residue left requires solvent extraction (known
as deasphalting) to recover the remaining valuable petroleum fraction. Atmospheric distillates
are the major source of petroleum fuels and vacuum distillates are the source of fuels, wax,
lubricating oil base stocks, bitumen, petroleum cokes, etc., mainly by secondary treatments like
extraction, thermal, and catalytic treatments.

II. Conversion process, of which coking and catalytic cracking (decomposing higher molecular
weight constituents of petroleum to produce lower molecular weight, normally more valuable,
products )
24
 Industrial chemistry IICHEM 3112

Finishing process: - of which hydrotreating to remove Sulphur from the crude oil components.

Hydrocracking: - Hydrocracking is a versatile catalytic refining process that upgrades petroleum

feed-stocks by adding hydrogen, removing impurities, and cracking to a desired boiling range.
Hydrocracking requires the conversion of a variety of types of molecules and is characterized by
the fact that the products are of significantly lower molecular weight than the feed.
Hydrocracking feeds can range from heavy vacuum gas oils and coke gas oils to atmospheric gas
oils. Products usually range from heavy diesel to light naphtha. Hydrocrackers are designed for
and run at a variety of conditions depending on many factors such as type of feed, desired cycle
length, expected product slate but in general they will operate ay range of conditions.

Hydrocracking converts the heavy feed stock to lower molecular weight products, removes
sulfur and nitrogen and saturates olefins and aromatics.

The organic sulfur is transformed into H2S, the nitrogen is transformed into NH3 and the oxygen
compounds (not always present) are transformed into H2O.

The reactions in hydrocracking can be classified in two categories: desirable and

undesirable. Desirable are the treating, saturation, and cracking reactions.

Hydrocracking reactions proceed through a bifunctional mechanism. A bifunctional mechanism

is one that requires two distinct types of catalytic sites to catalyze separate steps in the reaction

25
 Industrial chemistry IICHEM 3112

sequence. These two functions are the acid function, which provide for the cracking and
isomerization and the metal function, which provide for the olefin formation and hydrogenation.

In general, the hydrocracking reaction starts with the generation of an olefin or cycle olefin on a
metal site on the catalyst. Next, an acid site adds a proton to the olefin or cyclo-olefin to produce
a carbenium ion. The carbenium ion cracks to a smaller carbenium ion and a smaller olefin.
These products are the primary hydrocracking products. These primary products can react further
to produce still smaller secondary hydrocracking products.

Cracking, alkylation and reforming of coal

Cracking

The decomposition of bigger hydrocarbon molecules into simpler, low boiling hydrocarbons of
lower molecular weight is called cracking.

The basic processes introduced to bring about terminal decomposition of higher boiling streams
are known as cracking. In these processes, the higher boiling fractions are converted to lower
boiling products.

The gasoline obtained from the fractional distillation of petroleum, has the highest demand as a
motor fuel, but the yield of this fractions is only 20-30% (Crude oil) and also quality as straight-
run gasoline which is not good an_ hence is used only after proper blending. To overcome these
difficulties, the higher boiling fractions (e.g. fuel oil and gas oil) are converted into lower boiling
fractions gasoline (petrol) by cracking process.

The cracked gasoline gives better engine performance i.e., they are suitable for spark -ignition
engines of automobiles. In cracking process, higher saturated hydrocarbon molecules are
converted into simpler molecules such as paraffinic and olefinic hydrocarbons,

26
 Industrial chemistry IICHEM 3112

There are two methods of cracking in use

1. Thermal cracking 2. Catalytic cracking

Thermal cracking.

In this process, the heavy oil is subjected to high temperature and pressure, when the bigger
hydrocarbon molecules break down to give smaller molecules of the paraffins, olefins and
hydrogen. The cracked products are then separated by fractional distillation.

This process is carried out in liquid phase at a temperature of 4 75 - 530° C and under pressure of
100 kg/cm2 is called Liquid-phase thermal cracking or at a temperature of 600-650°C (heavy oil
is vapourised) and under a low pressure of 10-20 kg/cm2, such process is called Vapour-phase
thermal cracking.

Catalytic cracking

In this process, cracking is carried out in presence of a catalyst at lower temperature (300° C to
450° C) and pressures (l to 5 kg/cm2). The catalyst like aluminium silicate [Al2(SiO3)] or
alumina [A12O3] used in cracking gives higher yield and better quality of gasoline. There are
two types of catalytic cracking in use

Catalytic cracking is the most common cracking process, in which heavy feed stock or cuts are
Brocken down or changed by being heated and reacted with catalyst. The concept behind thermal
cracking is decomposition of higher molecular weight constituents of petroleum to produce low
molecular weight, normally more valuable, and products. Through catalytic processes more
gasoline having higher octane, less heavy fuel oils and light gases are produced by thermal
cracking. In thermal cracking process, a feed stock(e.g., gasoline) is fed to the fractionator with
the thermal reactivity to separate gasoline and light and heavy oil. The light oil is then fed to the
heater at 540 -5950C,a nd pressure of 350 – 700 pa; the light oil transforms to the vapor phase
and is sent to the soaker. If the feed stock is heavy oil, temperatures on the order of 400 – 480 0C
are used and higher pressure (350 -700pa) are used to maintain the feed stock in liquid phase,

27
 Industrial chemistry IICHEM 3112

then it is fed to soaker. The liquid and gas phase mix in the soaker and are sent to separator, with
the products coming out on the bottom as fuel oil and the light recycle back to fractionator.
Coking in the reactor is the main problem, when heavy oil is heated at high temperature. In many
refineries, cocking processes, which use high temperature and low temperature, have
superseded thermal cracking process. The principal application catalytic cracking is production
of high-octane gasoline, to supplement gasoline produced by distillation and other process.
Catalytic cracking also produce heating oil components and hydrocarbon feedstock, such as
propane and butane, for polymerization, alkylation, and petrochemical operations. The main
process used in catalytic cracking involves the use of fluidized bed units. The catalyst is usually
synthetic alumna or zeolite used as a catalyst. Compared to thermal cracking, the catalytic
cracking process:-

- Use a lower temperature

- Use a lower pressure
- More flexible
- The reaction mechanism is controlled by catalyst.

Feed stock for catalytic cracking includes: straight-run gas oil, vacuum gas oil, atmospheric
residuum, de-asphalted oil, and vacuum residuum coke inevitably builds up the catalyst overtime
and issue can be circumvented by continuous replacement of the catalyst or feed stock pretreated
before it is used by de-asphalting( remove coke precursors) hydro treating (that also prevents
excessive coke formation).

Hydro process use the principle that presence of hydrogen during a thermal reaction a petroleum
feed stock will terminate many of the coke- forming reactions and enhance yields of the lower-
boiling components such gasoline, kerosene, and jet fuel.

Hydroteating is carried out by charging the feed to the reactor, together with hydrogen in the
presence of catalyst, such as tungsten, nickel sulfide, cobalt molybdenum, alumna, oxide silica,
and platinum- alumna. Most process employ cobalt molybdenum catalyst that generally contains
about ten percent of molybdenum oxide and less than one percent of colt oxide supported on
alumna.

28
 Industrial chemistry IICHEM 3112

The reaction generally tacks place in the vapour phase, but depending on the application, may be
a mixed phase reaction. Generally it is more economical to hydrotreat high sulfur feed stocks
prior to catalytic cracking than hydrotreat the products from catalytic cracking. The advantages
are that

- Sulfur is removed from the catalytic cracking feed stock and corrosion is reduced in
the cracking units
- Carbon formation during cracking reduced, so that higher conversion result
- The cracking quality of gas oil fraction is involved

Hydrocracking is similar to catalytic cracking, with hydrogenation superimposed and with the
reaction tacking place either simultaneously or sequentially.

Hydrocracking was initially used to upgrade low value distillate feedstock, such as cycle oils
(high aromatic products from a catalytic cracker, which are usually not recycled to extinction for
economic reason), thermal and cooker gas oils and heavy cracked ant straight-run naphtha. These
feed stocks are difficult to process by either

Definition

29
 Industrial chemistry IICHEM 3112

 Petroleum is a mixture of gaseous, liquid, and solid hydrocarbon compounds that occur in
sedimentary rock deposits throughout the world and also contains small quantities of
nitrogen-, oxygen-, and sulfur-containing compounds, as well as trace amounts of
metallic constituents
 Crude petroleum is a mixture of compounds boiling at different temperatures that can be
separated into a variety of different generic fractions by distillation
 Petroleum occurs underground, at various pressures depending on the depth. Because of
the pressure, it contains considerable natural gas in solution. Petroleum underground is
much more fluid than it is on the surface and is generally mobile under reservoir
conditions because the elevated temperatures (the geothermal gradient) in subterranean
formations decrease the viscosity
 Petroleum is derived from aquatic plants and animals that lived and died hundreds of
millions of years ago.
 Petroleum (also called crude oil) is a mixture of gaseous, liquid, and solid hydrocarbon
compounds. Petroleum occurs in sedimentary rock deposits throughout the world and
also contains small quantities of nitrogen-, oxygen-, and sulfur-containing compounds, as
well as trace amounts of metallic constituents.


30